Dyestuffs and process of making same



Patented Oct. 29, 1940 UNlTED STATE DYESTUFFS AND PROCESS OF MAKING SAME Charles Graenacher, Riehen, and Richard Sallmann, Bottmingen, Switzerland, assignors to the firm Society of Chemical Industry in Basle,

Basel, Switzerland No Drawing. Application May 26,

' 276,025. In Switzerland May 31,

22 Claims.

This invention relates to the manufacture of valuable dyestuiTs by producing according to known methods dyestuffs of the general formula {(1 wherein R is the residue of a dyestufi, R1 is a member selected from the group consisting of wherein. a: has the signification defined in the preceding paragraph and R1 stands for hydrogen or an alkyl radical, substituted if desired, which are derived from azo dyestuffs, for example hydroxyazo dyestuifs, aminoazo dyestuffs having tertiary amino-groups, azo dyestuffs containing pyrazolone rings, or from anthraquinone dyestufis. An example of an azo dyestuff having a tertiary amino-group which may he used as parent material for the present invention is the azo dyestufl' from diazotized meta-aminobenzamide, and methylketol.

As groups determining the solubility of the dyestuff in Water there may be named onium-groups, for instance quaternary ammonium groups or ternary sulfonium groups, further amino and imino groups in the form of salts, for example thiourea residues, further carboxylic acid, sulfonic acid, thiosulfuric acid and sulfuric .acid ester groups.

By the expression heteroatoms there are to be understood as usual such atoms which are different from carbon atoms and which may be a member of a hetero-cycle, as is the case With oxygen, sulfur or nitrogen. The hetero-atoms oxygen, sulfur and nitrogen may also be defined as atoms of elements contained in the 5th and 1939, Serial No.

s PATENT mice 6th group' of the periodic system of the elements,

the atomic Weight of which is not and is practically an even n sion practically means in atomic weights round oii to be used for practical purposes instead of values higher than 32 umber. The expesthis case that the even numbers may the exact If the dyestuffs used as'parent materials contain already a carboxylic acid at least one free hydrogen converted into a group namely into the group amide group having atom, they maybe wherein R1 stands for hydrogen or alkyl, 11 stands for a quaternary nitrogen atom and 2 stands for a monoval'ent anion, by

treatment with salts of mixtures of tertiary amlnes and organic carboxylic acid anhydr hyde, if desired in ides, as well as with formaldethe presence of free tertiary amines. The N-methylol carboxylic acid amides obtainable'in known manner may be caused to react with salts or addition products of tertiary amines so as to form quaternary ammonium salts,

preferably in the presence of As tertiary amines for free tertiary amines.

the reactions indicated in the foregoing paragraph there may be named for example trimethylamine,

dimethylaniline, pyridine, '5

ethylcyclohexylamine,

C-alkylpyridine, or quinoline. of the tertiary amines propose ceding paragraph there are triethylamine, di-

Among the salts d in the last presuitable for the reaction for example pyridinehydrochloride, pyri dinehydrobromide, pyridine sulfonate and pyridine oxalate. As addition products of inorganic from sulfurdioxide for sulfu question. Formaldehyde is its polymeric modification,

anhydrides those made rtrioxide come into used preferably in for example parametanitrobenzene namely into the group wherein R1, n and 2 have the signification stated in the last paragraph but one, consists in transforming the carboxylic acid amide into the group lil OHrhalogen R1 and then allowing a tertiary amine, for example a tertiary amine named in the last preceding paragraph, to react with this group. The halogen compounds necessary for this reaction are obtainable in known manner from the carboxylic acid amides having at least one hydrogen atom at the nitrogen atom of the carboxylic acid amide group, by means of hydrogen halides and formaldehyde. This reaction is preferably conducted in the presence of a solvent, for instance, benzene. It is to be recommended that water produced during the reaction should be continuously removed, for example as an azeotropic mixture with the solvent or with aid of a substance that unites with water, for instance anhydrous magnesium sulfate. For

example the amide and the para-formaldehyde may be suspended in boiling benzene and hydrogen chloride introduced, the eliminated Water being distilled in admixture with benzene. The union of the halogen methyl compound with the tertiary amine may be procured in known manner, for instance by allowing them to stand together at room temperature or while moderately heating.

A further possibility for converting a carboxylic acid amide group containing at least one free hydrogen atom already present in the dyestuffs to be used as parent materials, into a group of the general formula R1 namely into the group I R1 2 R:

wherein R1 is hydrogen or alkyl,

is the radical of a secondary base and z is a monovalent anion, consists in transforming the carboxylic acid amide group in known manner into the N-methylol-carboxylic acid amide group, allowing a secondary amine, for example dimethylamine, diethylamine, diethanolamine, N-metliyl-cyclohexylamine or piperidine to react with this group and then adding an acid, for instance hydrochloric acid, formic acid, or acetic acid.

It is further possible to convert a carboxylic acid amide group containing at least one free hydrogen atom already present in the dyestuffs to be used as parent materials, into a group of the general formula wherein R1 is hydrogen or alkyl and m is the radical of a thiourea, if desired in the form of a salt. For example the corresponding carboxylic acid- N -methylolamides may be caused to react for this purpose with thiourea according to the process of application Serial No. 251,848, filed January 19, 1939, appropriately in the presence of alcoholic hydrochloric acid and by moderately heating, preferably by using a solvent such as acetone.

If the dyestuffs to be used as parent materials contain a suitable substituent, for example amino or hydroxy groups, the group wherein R1 and 1c have the significance given in the first paragraph, may be introduced into the substituent, preferably by means of an alkylene bridge. Reactive dyestuifs, such as hydroxyazodyestuffs of the benzene series or amino-anthraquinones, for example 1:4-di-(para-aminophenyl) -amino-anthraquinone, may thus be caused to react with amides of halogen carboxylic acids, for instance chloroacetic acid amide, p-chloropropionic acid amide or a-bromobutyric acid amide, and the carboxylic acid amide group which must contain at least one free hydrogen atom at the nitrogen atom may be converted in the manner described above into the group wherein R1 and a: have the significance given in the first paragraph.

According to the present invention dyestuffs containing the group I]TCHz-I wherein R1 and ac have the significance given in the first paragraph, may also be produced by coupling dia zonium. comp'Q md QQnlP capable, of coup n nta n the'gmup', v I

1 wo en;

for example with Quaternary ammonium compounds obtainable asudescribed above fromaromatic hydroxycarboxylic" acid methylolamides,

such as salicyliqacidmethylolamide.

The application: of" the dyestuffs obtained according to the present invention may be effected in such a manner that the material is treated in such solutions or dispersions of the dyestuffs in question which contain preferably catalysts such as weak acids or acid salts (formic acid, acetic acid, tartaric acid), for instance'at 30-60", and then heated, for example to -120 C. in the course of 1-2 hours. Further it is appropriateto add to the dye-baths salts of weak acids, for example sodium acetate, ,whereby injuries, of; the fiber are avoided. It isgadvantageoustodry the dyed materialbefore heating, appropriately at a low temperature.

It is also possible to fix, to .the fiber dyestuff components capable bf; coupling, on diazotizable coupling components which contain the above mentioned group 3 instead of dyestuffs with til er group I r n-r I R1) i V flu (R1 and :1: having the significance. .stated inthe 1st paragraph) is linked to a reactive radical, for example to an .alkyl, radical havinggreactive halogen atoms; maybe brought-onto the fiber and fixed thereon by heating, whereupon the reactive group is exchanged for dyestufi radicals. Thus the cellulose fiber treated with a compound of the formula I o ClCHz-C may be after-treated for example with aminoanthrachinones. r 1 J 5 The dyestuffs of the presentirivention may be used for dyeing vegetable and animal fibrous ma terials or artificially produced fibers, such as cellulose or materials containing cellulosefor in cellulose fiber, and the stance cotton, viscose rayon, copper rayon, paper, wool, silk and mixed fibrous materials, for example in the form of threads or fabrics. Moreover materials of artificial fibers which contain cellulose or cellulose derivatives or protein substances may be treated.

Dyeings produced withdyestuffs of the present invention are characterized by good fastness properties, particularly by good fastness to washing. It is very probable-that during heating a reaction occurs between the fiber, for example the group I NCHaa:

wherein R1 and a: have the significance stated in the first paragraph, existing in the dyestuffs. Probably the radical a: lending solubility to water is split off, whereas the group parts by weight toparts by volume is that which exists between the kilo and the liter. I

trample 1 arts of -.dyestuff pigment from ,diazotiz'ed para-aminobenzoic acid .amide and fi-n'aphthol are solved in-35 After, addition of 0.2 parts, of paraformaldehyde the ,whol-e'is heatedfor 35f1'ninutes on the water bath while stirring. There is then added 1.2 parts o fpyridine hydrochloride andheating is continued for 3 hoursat the same temperature. On cooling the dyestufi' of the formula which is soluble in water crystallises in the form parts by ,volume of pyridine.

of smallslender needles. After filtering and drying'it is obtained in the form of. an orangered .powderlwhich dissolves easily in water and dyes cotton'directly orange red. For this purpose cotton fabric is dyed with 2 per cent of the weight of the fiber of the above described quaternary pyridiniumchloride in presence of an equivalent quantity of sodium ac etate. v

The cotton preferably dried at a low temperature is heated for 1'-2 hours at 115-120 C. There is thus obtained a dyeing of a high" degree of fastness to washing. By the after-treatment by heat the fastness to washing is strongly increased as compared with that of the dyeing which has not been after-treated.

Instead of the above indicated carboxylic acid 'a'm'ide the corresponding amides in- -which' one hydrogen atom of the carboxylic acid amide group is replaced by methyl, ethyl, propyl, may be used. Instead of pyridine triethyl amine may be used.

5 Example 2 3.2 parts of a dyestuff pigment from diazotized aniline and 1-phenyl-3'-carboxylic acid amide-3- methylpyrazolone are heated together with 1.4

parts of pyridinehydrochlonde, 60 parts by volume of pyridine and 0.4 part of paraformaldehyde on the boiling water bath for 4 hours while stirring. The dyestuff first passes into solution and after a time the new pyridiniumchloride crystallises.

After filtering and removing the pyridine the new dyestuif of the formula is obtained in the form of a yellow crystalline powder freely soluble in water. The new dyestuff may be applied in the following manner: Cotton fabric is dyed with 2 per cent of the weight of the fiber of the above described dyestufi in presence of an equivalent quantity of sodium acetate. The cotton preferably dried at a low temperature is heated at 115-120 C. for 1-2 hours. The dyeing thus obtained is of high fastness to washing. By after-treatment by heat the fastness to washing is strongly increased as compared with that of the dyeing which has not been after-treated.

It is further possible to use the N-monoalkylsubstituted carboxylic acid amides instead of the above mentioned unsubstituted amide.

( Example 3 2.6 parts of the dyestuff from diazotized paraaminobenzamide and para-cresol are dissolved in 30 parts by volume of hot pyridine. To this so- F4 lution are added while stirring 0.4 part of paraformaldehyde and 1.4 parts of pyridine hydrochloride, and the whole is heated for 3 hours on the boiling water-bath. On cooling the new dyestuff of the formula R Cotton fabric is handled in an aqueous solution containing 5-10 per cent of the quaternary pyridinium chloride of the formula OH O C Cl obtainable from p-oxynaphthoic acid amide formaldehyde and pyridine hydrochloride in presence of pyridine, sodium acetate and acetic acid being added; the impregnated material is squeezed and dried. After it has been heated for 1-2 hours I at 120 C. the material may be washed with boiling hot sodium carbonate solution of 2 per cent strength and treated with a. diazotized amine to produce a dyeing extraordinarily fast to Washing.

Example 5 Cotton fabric is treated in the manner described in Example 4 with a solution of the quaternary pyridium chloride of the formula obtainable from para -(p hydroxynaphthoyl) aminobenzamide with formaldehyde and pyridine hydrochloride in presence of pyridine. The fabric thus treated and further treated as described in Example 4 may be dyed extraordinarily fast to washing by means of diazotized amineJ Example 6 is a feebly yellow crystalline mass which is freely soluble in water and decomposes gradually when boiling the aqueous solution.

10 parts of this condensation product are dissolved in parts by volume of distilled water. After addition of 8 partsof crystallized sodium acetate and 0.6 part by volume of formic acid some skeins of cotton are entered into this solution. After squeezing or centrifuging the skeins are dried at 5060 C. and then heated to 115 C. in the course of 3 hours.

By treating the material with a hot soap solution and rinsing with boiling water that part of the condensation product is removed which is fixed mechanically.

A sample of the cotton treated in such a manner is dyed an intensive orange color after reduction with an alkaline hydrosulfite solution, rinsing, diazotizing and coupling with ,B-naphthol, which dyeing is fast to washing.

Example 7 10 parts of the dyestufi from diazotized paraamino-benzamide and s-naphthol are heated to 100 C. with 60 parts by volume of pyridine and 4 parts of para-formaldehyde, while stirring,

and sulfur dioxide is passed through this mixture during 3 hours. After cooling the whole is resinous becomes gradually-powdery. The new dyestufi which corresponds ver-yprobably to, the formula dissolves in hot water, butafter boilingftl i e solution for a short time the dyestuff is separated in jelly-like form.

Earcmigalet 3.9 parts of the dyestuff from diazotized 'anthranilic acid-ethylester and the 1-phenyl-3- methylpyrazolone carboxylic acid; amide-(3) are heated for 4 hours on the vaporbath with 60 parts by volume, of pyridine, 0.4 partof paraformaldehyde and 1x4, parts of pyridine hydrochloride, while stirring. After cooling the new dyestufi of the formula wherein R representsthe radical of :1 a dyestuifselected from a group consisting of radicals of azo and anthraquinone dyestuffs, R1 stands for a member selected from'the group consisting of hydrogen and alkyl and 0: stands for a member of the group consisting. of quaternary ammonium groups, ternary sulfonium groups, amino and imino groups in the form of salts, thiourea 'resie dues'in the form of salts, "carboxylic acid, sul fonic acidythiosulfuric acid and sulfuric. acid ester groups and is united withthe group by a member of the group consisting "of'nitrogen atoms and sulfur atoms, which dyestuffs are decomposed when their aqueous solutions are boiled. I

2. A zo dyestuffs of the formula RC\ lTT-CHr-x R1 wherein R represents the radical of an azo-dyestuff, R1 stands forf a member selected from the group consisting of hydrogen and alkyl and :1: stands for a member of the group consisting of quaternary ammonium groups, ternary sulfonium groups, amino and imino groups-in the form of salts, thiourea residues inthe'form of salts, carboxylic acid, sulfonicacid, thiosulfuric acid and sulfuric acid-ester groups and is united with the CH2- group by a member of the group consisting of nitrogen atoms'and sulfur atoms, which dyestuffs are decomposed when their aqueous so lutions are boiled.

3. A20 dyestuffs of the formula NHCHr-13 wherein R, represents the radical of an azo dyestuff and r stands for a member of the group consisting of quaternary ammonium groups, ternary sulfonium groups,.amino and imino groupsin the form of salts, thiourea residues in the form of salts, .carboxylic acid, sulfonic acid, thiosulfuric acid and sulfuric acid ester groups and is united with the -CH2 group by a member of the group consisting of nitrogen atoms and sulfur atoms, which dyestuffs are decomposed when their aqueous solutions are boiled.

4. Azodyestuffs of theformula NH-CHz---a;

wherein It represents the radical of an hydroxyazo dyestuff and 1: stands for a member of the group consisting of quaternary ammonium groups, ternary sulfonium groups, amino and imino groups in'the form of salts, thiourea residues in the form of salts, carboxylic acid, sulfonicacid, thiosulfuric acid and sulfuric acid ester groups and is united with the -CH2 group by a member of the group consisting of nitrogen atoms and sulfur atoms, which dyestuffs are decomposed when their aqueous solutions are boiled.

5. A20 dyestuifs of the formula NHCHznz wherein Rrepresents the residue of an hydroxyazo dyestuff, n stands for a quaternarynitrogen I atom derived from a member of the group con- -sisting of trimethylamine, triethylamine, di-

wherein R represents the radical ofa hydroxyazo dyestuff and .2 stands for a monovalent anion which dyestuffs are decomposed when their aqueous solutions are boiled. 7. The hydroxyazo dyestuff of the formula which dyestuff is decomposed when its aqueous 15 solution, is boiled, an insoluble compoundbeing formed.

8. The hydroxyazo dyestuff of the formula which dyestuff is decomposed when its aqueous solution is boiled, an insoluble compound being formed. 1

30 9. A20 dyestuffs of the formula wherein R represents the radical of an azo-dyestuff containing a pyrazolone ring and 9: stands for a member of the groupconsisting of quarternary ammonium groups, ternary sulfonium 40 groups, amino and iminogroups in the form of salts, thiourea residues in the form of salts, carboxylic acid, sulfo-nic acid, thiosulfuric acid and sulfuric acid ester groups and is united with the y CI-I- group by a member of the group'consistdyestuffs are decomposed when their aqueous solutions are boiled.

10. A20 dyestuffs of the formula wherein R represents the radical of'an azo dyestuif containing a pyrazolonering and 2 stands for a monovalent anion which dyestuffs are dea ing of nitrogen atoms and sulfur atoms; which 75 composed when their aqueous solutions are boiled.

12. The azo. dyestuff of the formula which dyestufi is decomposed when its aqueous solution is boiled, an insoluble compound being formed.

13. The manufacture of dyestuffs of the general formula lII-CH:'n2 R1 wherein R represents the radical'of adyestufi selected from the group consisting of'radical's of" azo and anthraquinone dyestuffs, R1 stands for a member selected from the'groupconsisting of hydrogen and alkyl, 'n stands for-a quaternarynitrogen atom derived from a member of'the group consisting of trimethylamine, triethylamine, diethylcyclohexylamine, dimethylanillne, pyridine, C-alkylpyridine and quinoline, and 2 stands for a monovalent anion, which comprises reacting the correspondingcarboxylic acid. amides of the general formula 17IH R1 wherein R and R1 have the above indicated meaning, with formaldehyde and a salt of a tertiary amine in the presence of a freetertiaryamine- 14. The manufacture of-dyestuffsofthegeneral formula wherein R represents 1 the; radical of a: dyestufi selected from the group consisting of radicals of azo and anthraquinone dyestuffs, n stands for a quaternary nitrogen atom derived from amember of the group consisting of trimethylamine, triethylamine, diethylcyclohexylamine, dimethylaniline, pyridine, C-alkylpyridine and quinoline and 2 stands for a monovalent anion, which comprises reacting the' corresponding: carboxylic acid amide of the general formula,

wherein R has the aboveindicatedmeaning, with formaldehyde and asalt of "a tertiary amine in,

the presence of'a free tertiary amine.

15. The manufacturejof dyestuffs of. thegeneral formula.

wherein R has the above'indicated meaning, with formaldehyde and a salt of a; tertiary amine in the presence of a free tertiary amine.

16. The manufacture of dyestuffs of thegenere a1 formula i "f wherein R represents the radical of a hydroxyazo dyestuff, n stands for a quaternary nitrogen atom derived from a member of the group consisting of trimethylamine, triethylamine, diethylcyclohexylamine, dimethylaniline, pyridine, C-alkylpyridine and quinoline and 2 stands for a monovalent anion, which comprises reacting the corresponding carboxylic acid amide of the general formula wherein R has the above indicated meaning, with formaldehyde and a salt of a tertiary amine in the presence of a free tertiary amine.

1'7. The manufacture of dyestuffs of the general formula wherein R represents the residue of a hydroxyazo dyestuff and 2 stands for a monovalent anion,

which comprises reacting the corresponding carboxylic acid amide of the general formula wherein R has the above indicated meaning, with formaldehyde and a salt of pyridine in the presence of free pyridine.

18. The manufacture of the hydroxyazo dyestuff of the formula which comprises reacting the hydroxyazo dyestuff of the formula NH: H

with formaldehyde and pyridine hydrochloride in the presence of free pyridine. 1 I

19. The manufacture of the hydroxyazo dyestuff of the formula which comprises reacting the hydroxyazo dyestufl of the formula v NH: 0 Ha with formaldehyde and pyridine hydrochloride in the presence of free pyridine.

20. The manufacture of dyestuffs of the general formula wherein R represents the radical of an azo dyestuff containing a pyrazolone ring, n stands for a quaternary nitrogen atom derived from a member of the group consisting of trimethylamine, triethylamine, diethylcyclohexylamine, dimethylaniline, pyridine, C-alkylpyridine and quinoline and 2 stands for a monovalent anion, which comprises reacting the corresponding carboxylic acid amide of the general formula wherein R has the above indicated meaning, with formaldehyde and a salt of a tertiary amine in the presence of a free tertiary amine.

21. The manufacture of dyestuffs of the general formula wherein R represents the radical of an azo dyestuff containing a pyrazolone ring and 2 stands for a monovalent anion, which comprises reacting the corresponding carboxylic acid amide of the general formula wherein R has the above indicated meaning, with formaldehyde and a salt of pyridine in the preswhich comprises reacting the azo dyestuff of the ence of free pyridine. formula 22. The manufacture of the azo dyestuff of the formula.

0 5 $Ha C\ C=N\ NHCH:N/ Q fir OH 15 0 l& \O C5115 with formaldehyde and pyridine hydrochloride 00m in the presence of free pyridine.

CHARLES GRAENACHER. RICHARD SALIMANN. 

